research communications
N-[6-amino-5-(benzo[d]thiazol-2-yl)-3-cyano-4-methylsulfanyl-2-oxo-1,2-dihydropyridin-1-yl]-4-methylbenzenesulfonamide dimethylformamide monosolvate
ofaChemistry Department, Faculty of Science, Helwan University, Cairo, Egypt, and bInstitut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, D-38106 Braunschweig, Germany
*Correspondence e-mail: p.jones@tu-bs.de
In the title compound, C21H17N5O3S3·C3H7NO, the toluenesulfonamide ring and the combined ring system involving the pyridone and benzothiazole rings subtend an interplanar angle of 39.86 (4)°. The pyridone and benzothiazyl rings are linked by the intramolecular hydrogen bond N—Hamine⋯Nthiazole. The DMF O atom accepts two classical hydrogen bonds. The molecules are linked by hydrogen bonds and an S⋯O contact to form layers parallel to the bc plane.
Keywords: crystal structure; 2-pyridone; benzothiazole; dimethylformamide.
CCDC reference: 1582798
1. Chemical context
Cyanoketene dithioacetals are versatile synthetic intermediates (Elgemeie et al., 2003a, 2015) that have been utilized as building blocks for the synthesis of a wide range of (Elgemeie et al., 2009, 2017a); they are also of general interest in pharmaceutical chemistry (Elgemeie & Abou-Zeid, 2015; Elgemeie et al., 2016). Recently, we have described the synthesis of various antimetabolites starting from cyanoketene dithioacetals and related compounds, viz. cyanoketene S,S-acetals (Elgemeie, Mohamed, 2006), cyanoketene N,S-acetals (Elgemeie et al. 2017b), and cyanoketene N,N-acetals (Elgemeie et al., 2003b). As a part of this programme, the reaction of 2-(benzo[d]thiazol-2-yl)-3,3-bis(methylthio)acrylonitrile (1) with N-(2-cyanoacetyl)-4-methylbenzenesulfonohydrazide (2) was investigated. The reaction between 1 and 2 in KOH–DMF gives an adduct for which four possible isomeric structures were considered (structures 3–6). Spectroscopic methods did not allow us to identify the product unambiguously and therefore the X-ray was determined, confirming the exclusive presence of structure 6 in the solid state. The formation of 6 from the reaction of 1 and 2 is assumed to proceed via initial addition of the active methylene carbon atom of 2 to the double bond of 1, followed by elimination of CH3SH and via addition of the NH group to the cyano group of benzothiazole to give the favoured, kinetically and thermodynamically controlled product 6. The 1H NMR spectra of the product revealed the presence of an amino group at δ = 8.84 p.p.m. and a pyridine methylthio group at δ = 2.45 p.p.m. in solution. Compound 6 and its derivatives showed interesting preclinical biological results and are currently being patented (Elgemeie et al., 2017c).
2. Structural commentary
The solid-state structure of 6 is shown in Fig. 1, the structure analysis thereby confirming the nature of the product. The molecule essentially consists of two planes; the toluenesulfonamide ring and the combined ring system involving the pyridone and benzothiazole rings. The former has a r.m.s. deviation of 0.04 Å and the latter of 0.01 Å (including all direct substituents), and the interplanar angle is 39.86 (4)°. The pyridone and benzothiazyl rings are held coplanar by the intramolecular hydrogen bond N4—H03⋯N3 (Table 1). The contact N4—H02⋯N1 might also be classified as a hydrogen bond, with H⋯N 2.24 (2) Å, but its angle is only 105.7 (15)°. The nitrogen N4 is planar (angle sum 359.7°) but N1 is pyramidalized (343.9°).
3. Supramolecular features
The oyxgen atom of the dimethylformamide accepts two classical hydrogen bonds. The clearest packing feature is the formation of layers parallel to the bc plane (Fig. 2), in which the hydrogen bonds H02⋯O99, H7⋯O3ii and H97C⋯N5iv are involved (Table 1), together with the short contact S1⋯O3(x, 1 + y, z) 3.2662 (10) Å. The hydrogen bond H01⋯O99i connects the layers in the third dimension.
4. Database survey
The 2-pyridone ring displays the usual features of a narrow angle at nitrogen and a wide angle at the carbonyl carbon (Table 2). A database search gave 555 hits (745 values) for the 2-pyridone ring, with average angles of 123.9° at nitrogen and 115.3° at C=O. No other structures could be found in which a 2-pyridone ring is attached at the 5-position to the C2 atom of a thiazol ring.
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5. Synthesis and crystallization
2-(Benzo[d]thiazol-2-yl)-3,3-bis(methylthio)acrylonitrile (1) (2.78 g, 0.01 mol) was added to a solution of N-(2-cyanoacetyl)-4-methylbenzenesulfonohydrazide (2) (2.53 g., 0.01 mol) in dry DMF (30 ml) containing pulverized potassium hydroxide (0.56 g, 0.01 mol). The reaction mixture was refluxed with stirring for 2 h (TLC monitoring). After cooling, the reaction mixture was poured into ice-cold water and neutralized with HCl. The solid product was filtered off, washed with water, and dried. It was further purified from hot ethyl acetate: petroleum ether (1:1). The precipitated solid was crystallized from DMF to give yellow crystals, m.p. = 494 K, yield 78%.
IR (KBr, cm−1): ν 3393, 3208 (NH, NH2), 3072 (ArCH), 2922 (CH3), 2210 (CN), 1677 (CO), 1594 (C=N), 1350, 1170 (O=S=O); 1H NMR (400 MHz, DMSO-d6): δ 2.42 (s, 3H, CH3), 2.45 (s, 3H, SCH3), 7.42 (d, J = 8 Hz, 2H, C6H4), 7.49 (t, J = 8 Hz, 1H, benzothiazole H), 7.56 (t, J = 8 Hz, 1H, benzothiazole H), 7.71 (d, J = 8 Hz, 2H, C6H4), 8.06 (d, J = 8 Hz, 1H, benzothiazole H), 8.13 (d, J = 8 Hz, 1H, benzothiazole H), 8.84 (br, 2H, NH2), 11.44 (s, 1H, NH). Analysis calculated for C21H17N5O3S3 (483.59): C 52.16, H 3.54, N 14.48%; found: C 52.11; H 3.48; N 14.50%; MS m/z (%): 484 (M+1, 1.03%), 384 (84%), 356 (100%), 283 (60%), 117 (77%).
6. Refinement
Crystal data, data collection and structure . NH hydrogen atoms were refined freely. Methyl hydrogen atoms were refined as idealized rigid groups allowed to rotate but not tip (AFIX 137), with C—H 0.98 Å and H—C—H 109.5°. Other hydrogen atoms were included using a riding model starting from calculated positions (C—Haromatic 0.95, C—Hmethine 1.00 Å) with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for all others.
details are summarized in Table 3
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Supporting information
CCDC reference: 1582798
https://doi.org/10.1107/S2056989017015778/hg5500sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017015778/hg5500Isup2.hkl
Data collection: CrysAlis PRO (Rigaku OD, 2015); cell
CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015\bbr01); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C21H17N5O3S3·C3H7NO | Z = 2 |
Mr = 556.67 | F(000) = 580 |
Triclinic, P1 | Dx = 1.450 Mg m−3 |
a = 9.9916 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.7805 (6) Å | Cell parameters from 19857 reflections |
c = 11.9776 (6) Å | θ = 2.3–30.6° |
α = 88.809 (4)° | µ = 0.34 mm−1 |
β = 79.159 (4)° | T = 100 K |
γ = 67.245 (5)° | Tablet, yellow |
V = 1274.80 (12) Å3 | 0.5 × 0.4 × 0.2 mm |
Oxford Diffraction Xcalibur Eos diffractometer | 7630 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 6682 reflections with I > 2σ(I) |
Detector resolution: 16.1419 pixels mm-1 | Rint = 0.036 |
ω–scan | θmax = 31.1°, θmin = 2.3° |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015) | h = −14→14 |
Tmin = 0.972, Tmax = 1.000 | k = −16→16 |
68326 measured reflections | l = −17→17 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.033 | Hydrogen site location: mixed |
wR(F2) = 0.082 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0337P)2 + 0.772P] where P = (Fo2 + 2Fc2)/3 |
7630 reflections | (Δ/σ)max = 0.001 |
350 parameters | Δρmax = 0.61 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.20917 (3) | 1.05419 (3) | 0.44384 (2) | 0.01311 (6) | |
C2 | 0.17424 (12) | 0.91906 (10) | 0.43367 (10) | 0.0117 (2) | |
N3 | 0.13892 (11) | 0.90316 (9) | 0.33646 (8) | 0.01298 (18) | |
C3A | 0.13978 (12) | 0.99549 (11) | 0.26319 (10) | 0.0130 (2) | |
C4 | 0.10933 (14) | 1.00118 (12) | 0.15352 (10) | 0.0165 (2) | |
H4 | 0.086143 | 0.938809 | 0.122941 | 0.020* | |
C5 | 0.11382 (14) | 1.10006 (12) | 0.09052 (11) | 0.0183 (2) | |
H5 | 0.094063 | 1.105310 | 0.015622 | 0.022* | |
C6 | 0.14719 (14) | 1.19255 (12) | 0.13597 (11) | 0.0185 (2) | |
H6 | 0.148137 | 1.260042 | 0.091474 | 0.022* | |
C7 | 0.17885 (14) | 1.18784 (11) | 0.24436 (11) | 0.0167 (2) | |
H7 | 0.201612 | 1.250566 | 0.274740 | 0.020* | |
C7A | 0.17590 (13) | 1.08692 (11) | 0.30715 (10) | 0.0134 (2) | |
C8 | 0.18455 (12) | 0.82947 (10) | 0.52233 (10) | 0.0113 (2) | |
C9 | 0.21641 (12) | 0.84103 (10) | 0.63037 (10) | 0.0119 (2) | |
C10 | 0.22112 (13) | 0.75420 (11) | 0.71150 (10) | 0.0130 (2) | |
C11 | 0.19296 (13) | 0.64662 (11) | 0.69151 (10) | 0.0126 (2) | |
C12 | 0.16105 (12) | 0.72035 (10) | 0.49822 (9) | 0.0112 (2) | |
C13 | 0.25168 (14) | 0.76681 (11) | 0.82143 (11) | 0.0161 (2) | |
C14 | 0.44732 (16) | 0.90452 (15) | 0.64337 (18) | 0.0375 (4) | |
H14A | 0.482909 | 0.832100 | 0.688175 | 0.056* | |
H14B | 0.484276 | 0.965711 | 0.663453 | 0.056* | |
H14C | 0.483227 | 0.879848 | 0.562098 | 0.056* | |
S2 | 0.28523 (3) | 0.39958 (3) | 0.51130 (2) | 0.01363 (7) | |
S3 | 0.24867 (3) | 0.97028 (3) | 0.67335 (3) | 0.01445 (7) | |
O1 | 0.18556 (10) | 0.56948 (8) | 0.75942 (7) | 0.01650 (17) | |
O2 | 0.39814 (10) | 0.43053 (8) | 0.44172 (8) | 0.01993 (19) | |
O3 | 0.22015 (11) | 0.32617 (8) | 0.46616 (8) | 0.01989 (19) | |
N1 | 0.14142 (11) | 0.53246 (9) | 0.55209 (8) | 0.01215 (18) | |
H01 | 0.0686 (19) | 0.5236 (16) | 0.6018 (15) | 0.024 (4)* | |
N2 | 0.17243 (11) | 0.63362 (9) | 0.57965 (8) | 0.01120 (18) | |
N4 | 0.13014 (12) | 0.69607 (10) | 0.40197 (9) | 0.01497 (19) | |
H02 | 0.116 (2) | 0.6318 (18) | 0.3914 (16) | 0.031 (5)* | |
H03 | 0.118 (2) | 0.7536 (18) | 0.3545 (16) | 0.030 (5)* | |
N5 | 0.27764 (14) | 0.77140 (11) | 0.91037 (10) | 0.0249 (2) | |
C15 | 0.35093 (13) | 0.32693 (11) | 0.63125 (10) | 0.0142 (2) | |
C16 | 0.27838 (14) | 0.25780 (11) | 0.69169 (11) | 0.0162 (2) | |
H16 | 0.196647 | 0.250018 | 0.667958 | 0.019* | |
C17 | 0.32777 (14) | 0.20066 (11) | 0.78708 (11) | 0.0174 (2) | |
H17 | 0.278268 | 0.154275 | 0.829314 | 0.021* | |
C18 | 0.44894 (14) | 0.21006 (11) | 0.82216 (11) | 0.0173 (2) | |
C19 | 0.51825 (14) | 0.28051 (12) | 0.76017 (11) | 0.0184 (2) | |
H19 | 0.600293 | 0.288172 | 0.783499 | 0.022* | |
C20 | 0.46997 (13) | 0.33974 (11) | 0.66507 (11) | 0.0168 (2) | |
H20 | 0.517566 | 0.388092 | 0.623997 | 0.020* | |
C21 | 0.50385 (16) | 0.14328 (14) | 0.92318 (12) | 0.0247 (3) | |
H21A | 0.419338 | 0.152364 | 0.984240 | 0.037* | |
H21B | 0.567230 | 0.178318 | 0.950152 | 0.037* | |
H21C | 0.560779 | 0.055639 | 0.901004 | 0.037* | |
C97 | 0.20835 (19) | 0.51005 (15) | −0.00331 (12) | 0.0303 (3) | |
H97A | 0.105803 | 0.547512 | −0.014305 | 0.045* | |
H97B | 0.258431 | 0.429728 | −0.045575 | 0.045* | |
H97C | 0.259893 | 0.563981 | −0.031259 | 0.045* | |
C98 | 0.35300 (17) | 0.44892 (18) | 0.15100 (14) | 0.0356 (4) | |
H98A | 0.339323 | 0.441322 | 0.233601 | 0.053* | |
H98B | 0.400502 | 0.507200 | 0.129860 | 0.053* | |
H98C | 0.415656 | 0.368141 | 0.112343 | 0.053* | |
C99 | 0.08612 (15) | 0.51648 (12) | 0.19300 (11) | 0.0186 (2) | |
H99 | −0.003677 | 0.541604 | 0.165524 | 0.022* | |
N99 | 0.20970 (13) | 0.49363 (11) | 0.11715 (9) | 0.0198 (2) | |
O99 | 0.07862 (10) | 0.50763 (9) | 0.29665 (7) | 0.01853 (18) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.01528 (13) | 0.01090 (13) | 0.01511 (13) | −0.00706 (10) | −0.00348 (10) | 0.00176 (10) |
C2 | 0.0104 (5) | 0.0097 (5) | 0.0145 (5) | −0.0042 (4) | −0.0008 (4) | 0.0002 (4) |
N3 | 0.0147 (4) | 0.0121 (4) | 0.0126 (4) | −0.0060 (4) | −0.0022 (3) | 0.0015 (3) |
C3A | 0.0114 (5) | 0.0121 (5) | 0.0137 (5) | −0.0038 (4) | −0.0004 (4) | 0.0013 (4) |
C4 | 0.0173 (5) | 0.0168 (5) | 0.0156 (5) | −0.0069 (4) | −0.0032 (4) | 0.0016 (4) |
C5 | 0.0184 (6) | 0.0200 (6) | 0.0148 (5) | −0.0059 (5) | −0.0029 (4) | 0.0046 (4) |
C6 | 0.0188 (6) | 0.0156 (6) | 0.0195 (6) | −0.0062 (5) | −0.0020 (5) | 0.0059 (4) |
C7 | 0.0174 (5) | 0.0130 (5) | 0.0198 (6) | −0.0067 (4) | −0.0021 (4) | 0.0038 (4) |
C7A | 0.0124 (5) | 0.0122 (5) | 0.0143 (5) | −0.0042 (4) | −0.0013 (4) | 0.0020 (4) |
C8 | 0.0114 (5) | 0.0092 (5) | 0.0130 (5) | −0.0041 (4) | −0.0016 (4) | −0.0003 (4) |
C9 | 0.0108 (5) | 0.0108 (5) | 0.0139 (5) | −0.0041 (4) | −0.0017 (4) | −0.0015 (4) |
C10 | 0.0140 (5) | 0.0127 (5) | 0.0123 (5) | −0.0049 (4) | −0.0032 (4) | −0.0008 (4) |
C11 | 0.0133 (5) | 0.0126 (5) | 0.0108 (5) | −0.0039 (4) | −0.0023 (4) | −0.0005 (4) |
C12 | 0.0115 (5) | 0.0105 (5) | 0.0113 (5) | −0.0044 (4) | −0.0007 (4) | 0.0004 (4) |
C13 | 0.0178 (5) | 0.0139 (5) | 0.0172 (6) | −0.0060 (4) | −0.0053 (4) | 0.0001 (4) |
C14 | 0.0149 (6) | 0.0276 (8) | 0.0685 (12) | −0.0089 (6) | −0.0016 (7) | −0.0143 (8) |
S2 | 0.01854 (14) | 0.00982 (12) | 0.01155 (13) | −0.00509 (10) | −0.00151 (10) | −0.00011 (9) |
S3 | 0.01584 (13) | 0.01206 (13) | 0.01707 (14) | −0.00662 (10) | −0.00418 (10) | −0.00170 (10) |
O1 | 0.0234 (4) | 0.0140 (4) | 0.0126 (4) | −0.0076 (3) | −0.0040 (3) | 0.0024 (3) |
O2 | 0.0211 (4) | 0.0179 (4) | 0.0164 (4) | −0.0061 (4) | 0.0033 (3) | 0.0016 (3) |
O3 | 0.0315 (5) | 0.0121 (4) | 0.0181 (4) | −0.0088 (4) | −0.0089 (4) | −0.0005 (3) |
N1 | 0.0155 (5) | 0.0092 (4) | 0.0131 (4) | −0.0067 (4) | −0.0018 (4) | 0.0001 (3) |
N2 | 0.0153 (4) | 0.0090 (4) | 0.0108 (4) | −0.0063 (3) | −0.0028 (3) | 0.0000 (3) |
N4 | 0.0237 (5) | 0.0127 (5) | 0.0129 (5) | −0.0107 (4) | −0.0062 (4) | 0.0025 (4) |
N5 | 0.0317 (6) | 0.0252 (6) | 0.0212 (6) | −0.0117 (5) | −0.0121 (5) | 0.0009 (5) |
C15 | 0.0168 (5) | 0.0100 (5) | 0.0139 (5) | −0.0038 (4) | −0.0017 (4) | 0.0002 (4) |
C16 | 0.0190 (6) | 0.0137 (5) | 0.0177 (6) | −0.0080 (4) | −0.0046 (4) | 0.0019 (4) |
C17 | 0.0210 (6) | 0.0139 (5) | 0.0172 (6) | −0.0073 (5) | −0.0030 (4) | 0.0025 (4) |
C18 | 0.0171 (5) | 0.0147 (5) | 0.0152 (5) | −0.0013 (4) | −0.0026 (4) | −0.0005 (4) |
C19 | 0.0130 (5) | 0.0194 (6) | 0.0208 (6) | −0.0040 (4) | −0.0030 (4) | −0.0009 (5) |
C20 | 0.0145 (5) | 0.0151 (5) | 0.0190 (6) | −0.0054 (4) | 0.0001 (4) | −0.0003 (4) |
C21 | 0.0214 (6) | 0.0284 (7) | 0.0198 (6) | −0.0041 (5) | −0.0063 (5) | 0.0065 (5) |
C97 | 0.0417 (9) | 0.0361 (8) | 0.0130 (6) | −0.0163 (7) | −0.0027 (6) | 0.0032 (5) |
C98 | 0.0233 (7) | 0.0561 (11) | 0.0247 (7) | −0.0136 (7) | −0.0018 (6) | −0.0001 (7) |
C99 | 0.0228 (6) | 0.0182 (6) | 0.0164 (6) | −0.0094 (5) | −0.0045 (5) | 0.0006 (4) |
N99 | 0.0238 (5) | 0.0229 (5) | 0.0126 (5) | −0.0098 (4) | −0.0021 (4) | 0.0011 (4) |
O99 | 0.0248 (5) | 0.0228 (5) | 0.0127 (4) | −0.0153 (4) | −0.0016 (3) | −0.0004 (3) |
S1—C7A | 1.7375 (12) | S2—N1 | 1.6678 (10) |
S1—C2 | 1.7677 (12) | S2—C15 | 1.7597 (12) |
C2—N3 | 1.3153 (15) | N1—N2 | 1.4020 (13) |
C2—C8 | 1.4706 (15) | N1—H01 | 0.888 (18) |
N3—C3A | 1.3848 (14) | N4—H02 | 0.84 (2) |
C3A—C4 | 1.3977 (17) | N4—H03 | 0.86 (2) |
C3A—C7A | 1.4013 (17) | C15—C20 | 1.3872 (17) |
C4—C5 | 1.3855 (17) | C15—C16 | 1.3955 (17) |
C4—H4 | 0.9500 | C16—C17 | 1.3875 (17) |
C5—C6 | 1.4031 (19) | C16—H16 | 0.9500 |
C5—H5 | 0.9500 | C17—C18 | 1.3970 (18) |
C6—C7 | 1.3880 (18) | C17—H17 | 0.9500 |
C6—H6 | 0.9500 | C18—C19 | 1.3948 (18) |
C7—C7A | 1.4005 (16) | C18—C21 | 1.5034 (18) |
C7—H7 | 0.9500 | C19—C20 | 1.3894 (18) |
C8—C9 | 1.4108 (16) | C19—H19 | 0.9500 |
C8—C12 | 1.4372 (15) | C20—H20 | 0.9500 |
C9—C10 | 1.3897 (16) | C21—H21A | 0.9800 |
C9—S3 | 1.7781 (12) | C21—H21B | 0.9800 |
C10—C13 | 1.4295 (16) | C21—H21C | 0.9800 |
C10—C11 | 1.4340 (16) | C97—N99 | 1.4536 (17) |
C11—O1 | 1.2213 (14) | C97—H97A | 0.9800 |
C11—N2 | 1.4132 (14) | C97—H97B | 0.9800 |
C12—N4 | 1.3124 (15) | C97—H97C | 0.9800 |
C12—N2 | 1.3851 (14) | C98—N99 | 1.4554 (19) |
C13—N5 | 1.1499 (17) | C98—H98A | 0.9800 |
C14—S3 | 1.7952 (15) | C98—H98B | 0.9800 |
C14—H14A | 0.9800 | C98—H98C | 0.9800 |
C14—H14B | 0.9800 | C99—O99 | 1.2343 (15) |
C14—H14C | 0.9800 | C99—N99 | 1.3242 (17) |
S2—O3 | 1.4317 (10) | C99—H99 | 0.9500 |
S2—O2 | 1.4326 (9) | ||
C7A—S1—C2 | 89.58 (6) | N2—N1—S2 | 117.20 (8) |
N3—C2—C8 | 121.49 (10) | N2—N1—H01 | 113.6 (11) |
N3—C2—S1 | 113.55 (8) | S2—N1—H01 | 113.1 (11) |
C8—C2—S1 | 124.95 (9) | C12—N2—N1 | 115.94 (9) |
C2—N3—C3A | 112.58 (10) | C12—N2—C11 | 125.63 (10) |
N3—C3A—C4 | 125.08 (11) | N1—N2—C11 | 117.88 (9) |
N3—C3A—C7A | 114.40 (10) | C12—N4—H02 | 121.2 (13) |
C4—C3A—C7A | 120.52 (11) | C12—N4—H03 | 114.9 (13) |
C5—C4—C3A | 118.33 (12) | H02—N4—H03 | 123.6 (18) |
C5—C4—H4 | 120.8 | C20—C15—C16 | 121.33 (11) |
C3A—C4—H4 | 120.8 | C20—C15—S2 | 120.72 (9) |
C4—C5—C6 | 120.82 (12) | C16—C15—S2 | 117.94 (9) |
C4—C5—H5 | 119.6 | C17—C16—C15 | 118.80 (12) |
C6—C5—H5 | 119.6 | C17—C16—H16 | 120.6 |
C7—C6—C5 | 121.60 (11) | C15—C16—H16 | 120.6 |
C7—C6—H6 | 119.2 | C16—C17—C18 | 121.22 (12) |
C5—C6—H6 | 119.2 | C16—C17—H17 | 119.4 |
C6—C7—C7A | 117.34 (12) | C18—C17—H17 | 119.4 |
C6—C7—H7 | 121.3 | C19—C18—C17 | 118.44 (11) |
C7A—C7—H7 | 121.3 | C19—C18—C21 | 121.38 (12) |
C7—C7A—C3A | 121.37 (11) | C17—C18—C21 | 120.17 (12) |
C7—C7A—S1 | 128.74 (10) | C20—C19—C18 | 121.46 (12) |
C3A—C7A—S1 | 109.88 (8) | C20—C19—H19 | 119.3 |
C9—C8—C12 | 116.48 (10) | C18—C19—H19 | 119.3 |
C9—C8—C2 | 125.41 (10) | C15—C20—C19 | 118.73 (11) |
C12—C8—C2 | 118.11 (10) | C15—C20—H20 | 120.6 |
C10—C9—C8 | 122.53 (10) | C19—C20—H20 | 120.6 |
C10—C9—S3 | 115.37 (9) | C18—C21—H21A | 109.5 |
C8—C9—S3 | 122.08 (9) | C18—C21—H21B | 109.5 |
C9—C10—C13 | 122.46 (11) | H21A—C21—H21B | 109.5 |
C9—C10—C11 | 122.30 (10) | C18—C21—H21C | 109.5 |
C13—C10—C11 | 115.24 (10) | H21A—C21—H21C | 109.5 |
O1—C11—N2 | 119.46 (11) | H21B—C21—H21C | 109.5 |
O1—C11—C10 | 127.10 (11) | N99—C97—H97A | 109.5 |
N2—C11—C10 | 113.44 (10) | N99—C97—H97B | 109.5 |
N4—C12—N2 | 116.83 (10) | H97A—C97—H97B | 109.5 |
N4—C12—C8 | 123.94 (11) | N99—C97—H97C | 109.5 |
N2—C12—C8 | 119.23 (10) | H97A—C97—H97C | 109.5 |
N5—C13—C10 | 176.92 (13) | H97B—C97—H97C | 109.5 |
S3—C14—H14A | 109.5 | N99—C98—H98A | 109.5 |
S3—C14—H14B | 109.5 | N99—C98—H98B | 109.5 |
H14A—C14—H14B | 109.5 | H98A—C98—H98B | 109.5 |
S3—C14—H14C | 109.5 | N99—C98—H98C | 109.5 |
H14A—C14—H14C | 109.5 | H98A—C98—H98C | 109.5 |
H14B—C14—H14C | 109.5 | H98B—C98—H98C | 109.5 |
O3—S2—O2 | 121.42 (6) | O99—C99—N99 | 125.03 (13) |
O3—S2—N1 | 102.99 (5) | O99—C99—H99 | 117.5 |
O2—S2—N1 | 106.32 (5) | N99—C99—H99 | 117.5 |
O3—S2—C15 | 106.76 (6) | C99—N99—C97 | 121.56 (12) |
O2—S2—C15 | 109.03 (6) | C99—N99—C98 | 121.18 (12) |
N1—S2—C15 | 109.88 (5) | C97—N99—C98 | 117.25 (12) |
C9—S3—C14 | 98.98 (6) | ||
C7A—S1—C2—N3 | −0.89 (9) | C2—C8—C12—N4 | −0.37 (17) |
C7A—S1—C2—C8 | 178.19 (10) | C9—C8—C12—N2 | −0.79 (15) |
C8—C2—N3—C3A | −178.06 (10) | C2—C8—C12—N2 | 179.01 (10) |
S1—C2—N3—C3A | 1.06 (13) | C10—C9—S3—C14 | 83.40 (11) |
C2—N3—C3A—C4 | 178.78 (11) | C8—C9—S3—C14 | −98.15 (12) |
C2—N3—C3A—C7A | −0.70 (14) | O3—S2—N1—N2 | −167.59 (8) |
N3—C3A—C4—C5 | 179.67 (11) | O2—S2—N1—N2 | −38.90 (9) |
C7A—C3A—C4—C5 | −0.89 (17) | C15—S2—N1—N2 | 78.95 (9) |
C3A—C4—C5—C6 | −0.39 (18) | N4—C12—N2—N1 | −3.39 (15) |
C4—C5—C6—C7 | 0.93 (19) | C8—C12—N2—N1 | 177.19 (10) |
C5—C6—C7—C7A | −0.15 (18) | N4—C12—N2—C11 | −174.61 (10) |
C6—C7—C7A—C3A | −1.15 (17) | C8—C12—N2—C11 | 5.97 (17) |
C6—C7—C7A—S1 | −179.72 (9) | S2—N1—N2—C12 | 103.12 (10) |
N3—C3A—C7A—C7 | −178.80 (11) | S2—N1—N2—C11 | −84.95 (11) |
C4—C3A—C7A—C7 | 1.70 (17) | O1—C11—N2—C12 | 172.21 (11) |
N3—C3A—C7A—S1 | 0.01 (13) | C10—C11—N2—C12 | −7.76 (16) |
C4—C3A—C7A—S1 | −179.49 (9) | O1—C11—N2—N1 | 1.15 (16) |
C2—S1—C7A—C7 | 179.17 (12) | C10—C11—N2—N1 | −178.82 (9) |
C2—S1—C7A—C3A | 0.47 (9) | O3—S2—C15—C20 | 152.17 (10) |
N3—C2—C8—C9 | −177.62 (11) | O2—S2—C15—C20 | 19.34 (12) |
S1—C2—C8—C9 | 3.36 (16) | N1—S2—C15—C20 | −96.82 (10) |
N3—C2—C8—C12 | 2.61 (16) | O3—S2—C15—C16 | −28.68 (11) |
S1—C2—C8—C12 | −176.41 (8) | O2—S2—C15—C16 | −161.51 (9) |
C12—C8—C9—C10 | −1.79 (16) | N1—S2—C15—C16 | 82.33 (10) |
C2—C8—C9—C10 | 178.44 (11) | C20—C15—C16—C17 | −0.33 (18) |
C12—C8—C9—S3 | 179.88 (8) | S2—C15—C16—C17 | −179.47 (9) |
C2—C8—C9—S3 | 0.10 (16) | C15—C16—C17—C18 | −0.79 (19) |
C8—C9—C10—C13 | −179.23 (11) | C16—C17—C18—C19 | 1.19 (18) |
S3—C9—C10—C13 | −0.79 (15) | C16—C17—C18—C21 | −177.66 (12) |
C8—C9—C10—C11 | −0.40 (18) | C17—C18—C19—C20 | −0.49 (19) |
S3—C9—C10—C11 | 178.04 (9) | C21—C18—C19—C20 | 178.35 (12) |
C9—C10—C11—O1 | −175.15 (12) | C16—C15—C20—C19 | 1.01 (18) |
C13—C10—C11—O1 | 3.76 (18) | S2—C15—C20—C19 | −179.87 (9) |
C9—C10—C11—N2 | 4.82 (16) | C18—C19—C20—C15 | −0.59 (19) |
C13—C10—C11—N2 | −176.27 (10) | O99—C99—N99—C97 | −178.03 (13) |
C9—C8—C12—N4 | 179.84 (11) | O99—C99—N99—C98 | 3.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H01···O99i | 0.888 (18) | 1.872 (18) | 2.7583 (13) | 175.7 (16) |
N4—H02···O99 | 0.84 (2) | 2.05 (2) | 2.8334 (14) | 154.6 (18) |
N4—H03···N3 | 0.86 (2) | 1.86 (2) | 2.5760 (15) | 139.9 (17) |
N4—H02···N1 | 0.84 (2) | 2.237 (19) | 2.5932 (14) | 105.7 (15) |
C7—H7···O3ii | 0.95 | 2.54 | 3.3161 (16) | 139 |
C20—H20···O2iii | 0.95 | 2.64 | 3.5605 (16) | 164 |
C97—H97C···N5iv | 0.98 | 2.59 | 3.504 (2) | 155 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y+1, z; (iii) −x+1, −y+1, −z+1; (iv) x, y, z−1. |
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